Threshold switching is a phenomenon where the resistivity of an insulating material changes and the insulator exhibits metallic behavior. This could be explained by phase transformation in oxide materials; however, this behavior is also seen in amorphous insulators. In this study, through an ex-situ experiment using transmission electron microscopy (TEM), we proved that threshold switching of amorphous NbO2 accompanies local crystallization. The change in I–V characteristics after electroforming was examined by evaluating the concentration profile. Atom probe tomography (APT) combined with in-situ TEM probing technique was performed to understand the threshold switching in amorphous NbO2. The local crystallization in amorphous NbO2 was validated by the observed difference in time-of-flight (ToF) between amorphous and crystalline NbO2. We concluded that the slower ToF of amorphous NbO2 (a-NbO2) compared with crystalline NbO2 (c-NbO2) is due to the resistivity difference and trap-assisted recombination.